EP0822191A1 - Préparation d'intermédiaires pour l'oxyde de norlabdane - Google Patents

Préparation d'intermédiaires pour l'oxyde de norlabdane Download PDF

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Publication number
EP0822191A1
EP0822191A1 EP97202021A EP97202021A EP0822191A1 EP 0822191 A1 EP0822191 A1 EP 0822191A1 EP 97202021 A EP97202021 A EP 97202021A EP 97202021 A EP97202021 A EP 97202021A EP 0822191 A1 EP0822191 A1 EP 0822191A1
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EP
European Patent Office
Prior art keywords
oxide
sclareol
process according
norlabdane
oxidation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP97202021A
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German (de)
English (en)
Other versions
EP0822191B1 (fr
Inventor
Paul Nicholas Davey
Laurence Sidney Payne
Chi-Lam Tse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Givaudan Nederland Services BV
Original Assignee
Quest International BV
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Priority to EP19970202021 priority Critical patent/EP0822191B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/92—Naphthofurans; Hydrogenated naphthofurans

Definitions

  • the present invention relates to the synthesis of the fragrance material 1,2,3a,4,5,5a,6,7,8,9,9a,9b-dodecahydro-3a,6,6,9a-tetramethylnaphto-(2,1-b)-furan, also known as (-)-norlabdane oxide.
  • (-)-Norlabdane oxide of formula (1) below, is a well known fragrance material. It is the most widely used material for providing an ambergris-type odour to perfumes and is sold under various trade names, notably as Amberlyn, Ambroxan, Ambrox or Amberoxide. A number of synthetic procedures for this compound have been published. Many use naturally occurring (-)-sclareol of formula (2) below as the starting material from which the norlabdane oxide is obtained in a multistep synthesis. All processes starting from sclareol have in common that they proceed via the diol of formula (3) below as an intermediate, which has to be cyclized to give compound (1). This cyclization requires considerable care to prevent the formation of the more thermodynamically stable iso-form of (1), which has inferior olfactive properties, and the elimination of the tertiary alcohol group.
  • the organic hydroperoxide used in step I is preferably a hydroperoxide derived from an aliphatic or alicyclic alcohol, particularly a tertiary alcohol.
  • Tert-butyl hydroperoxide is very suitable.
  • These hydroperoxides may be prepared in situ by using the corresponding alcohol as solvent or cosolvent for sclareol oxide and adding hydrogen peroxide to the solution.
  • the reaction is preferably carried out in the presence of a catalytic amount of iodine.
  • the reaction temperature may be chosen between 0 and 50°C, preferably between 10 and 30°C. After the reaction any excess peroxide may be removed according to usual procedures by treatment with a suitable reducing agent, such as a thiosulphate salt.
  • a suitable reducing agent such as a thiosulphate salt.
  • the 12-acetyl-norlabdane oxide is obtained in high yield as a mixture of 12-epimers which can be used in step II without any further purification or
  • the sclareol oxide used as the starting material in step I may be obtained by any of the methods described in the art.
  • a preferred, novel and improved method involves the oxidation of sclareol with ozone, followed by treatment with alkaline hydrogen peroxide.
  • This ozonolysis can be performed under usual ozonolysis conditions, using a temperature of -20 - +40°C, preferably +10 - +30°C, more preferably and for the sake of convenience at around room temperature (15-25 o C).
  • a solvent may be used which is usual for ozonolysis reactions such as a lower alcohol, a lower aliphatic acetate or methylene chloride, preferably a C1-C5 alcohol such as methanol or ethanol.
  • the hydrogen peroxide oxidation can be performed with dilute hydrogen peroxide, particularly 1-30% in water, in the presence of a suitable base, such as an alkaline or alkaline earth metal hydroxide, particularly NaOH or KOH. After the reaction any excess peroxide may be removed according to usual procedures by treatment with a suitable reducing agent, such as a thiosulphate salt. Sclareol oxide is obtained in high yield and can be used in step I without further purification.
  • a suitable base such as an alkaline or alkaline earth metal hydroxide, particularly NaOH or KOH.
  • the reaction with the organic peracid (step II) is carried out in a solvent which is inert to the reagent.
  • Aliphatic or alicyclic ethers are particularly suitable, such as tert-butyl methyl ether.
  • various organic peracids are suitable for the reaction, a lower (e.g. C1-C5) aliphatic peracid is preferred.
  • Peracetic acid is particularly suitable.
  • an anhydrous buffer salt should be present, such as sodium acetate, or preferably sodium formate.
  • the reaction can be carried out between 0 and 30°C, preferably, and for the sake of convenience at around room temperature (15-25 o C).
  • any excess peracid may be removed according to usual procedures by treatment with a suitable reducing agent, such as a thiosulphate salt.
  • a suitable reducing agent such as a thiosulphate salt.
  • Step I and II may be carried out successiveively without purification of the product of step I. They may even be carried out in one pot without isolation of the acetyl-norlabdane oxide. This also holds for the ozone oxidation of sclareol to sclareol oxide and step I. Even the total reaction sequence from sclareol to 12-acetoxy-norlabdane oxide may be carried out without purification of the intermediates, and even in one pot without isolation of the intermediates.
  • the 12-acetoxy-norlabdane oxide can be converted to (-)-norlabdane oxide by complex metal hydride reduction, particularly with LiAlH 4 /BF 3 -etherate as described in US-A-5,463,089 and 5,473,085.
  • a novel and very convenient process uses NaBH 4 in the presence a transition metal salt, particularly a transition metal halogenide such as ZnCl 2 , FeCl 3 , or CuBr. Sometimes this gives rise to a mixture of norlabdane oxide and diol (3). After separation of the mixture, the diol may be cyclized as described in the prior art.
  • a transition metal salt particularly a transition metal halogenide such as ZnCl 2 , FeCl 3 , or CuBr.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Compounds (AREA)
EP19970202021 1996-08-02 1997-07-02 Préparation d'intermédiaires pour l'oxyde de norlabdane Expired - Lifetime EP0822191B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19970202021 EP0822191B1 (fr) 1996-08-02 1997-07-02 Préparation d'intermédiaires pour l'oxyde de norlabdane

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP96305708 1996-08-02
EP96305708 1996-08-02
EP19970202021 EP0822191B1 (fr) 1996-08-02 1997-07-02 Préparation d'intermédiaires pour l'oxyde de norlabdane

Publications (2)

Publication Number Publication Date
EP0822191A1 true EP0822191A1 (fr) 1998-02-04
EP0822191B1 EP0822191B1 (fr) 2001-09-19

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EP19970202021 Expired - Lifetime EP0822191B1 (fr) 1996-08-02 1997-07-02 Préparation d'intermédiaires pour l'oxyde de norlabdane

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EP (1) EP0822191B1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000063200A1 (fr) * 1999-04-16 2000-10-26 Quest International B.V. Preparation d'oxyde de norlabdane
GR1004177B (el) * 2001-07-05 2003-03-05 Βιορυλ Χημικη Και Γεωργικη Βιομηχανια, Επιστημονικη Ερευνα Α.Ε. Νεα μεθοδος συνθεσης (-) δωδεκαυδρο-3α,6,6,9α,-τετραμεθυλοναφθο (1,2β) φουρανιου
EP1710224A1 (fr) 2005-04-05 2006-10-11 Symrise GmbH & Co. KG Procédé pour la préparation de cétones par ozonolyse
WO2007036381A1 (fr) 2005-09-28 2007-04-05 Symrise Gmbh & Co. Kg Preparation d'aldehydes par ozonolyse d'alcools d'allyle secondaires
MD3889C2 (ro) * 2008-05-19 2009-11-30 Институт Химии Академии Наук Молдовы Procedeu de obţinere a 11-bishomodrim-8(9)-en-12-onei
MD4209C1 (ro) * 2012-03-30 2013-10-31 Институт Химии Академии Наук Молдовы Procedeu de obţinere a sclareoloxidului

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3050532A (en) * 1959-06-19 1962-08-21 Reynolds Tobacco Co R Two stage oxidation of sclareol
EP0296564A2 (fr) * 1987-06-23 1988-12-28 Givaudan-Roure (International) S.A. Procédé pour la préparation de dodécahydro-3a,6,6,9a-tétraméthylnaphtho[2,1b]furanne et de dérivés d'haloéthyl-décaline
DE3942358A1 (de) * 1989-12-21 1991-06-27 Henkel Kgaa Verfahren zur herstellung von sclareolid
DE4123767A1 (de) * 1991-07-18 1993-01-21 Henkel Kgaa Verfahren zur herstellung von 8,12-oxido-13,14,15,16-tetranorlabdan
US5463089A (en) * 1994-07-22 1995-10-31 Quest International B.V. Preparation of ambrox
DE4439574A1 (de) * 1994-11-05 1996-05-09 Henkel Kgaa Verfahren zur Herstellung von 8alpha,12-Oxido-13,14,15,16-tetranorlabdan
EP0752423A1 (fr) * 1995-07-06 1997-01-08 Basf Aktiengesellschaft Procédé pour la préparation stéréosélective de (-)3a,6,6,9a-tétraméthyl-perhydronaphto(2,1-b)furanne

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3050532A (en) * 1959-06-19 1962-08-21 Reynolds Tobacco Co R Two stage oxidation of sclareol
EP0296564A2 (fr) * 1987-06-23 1988-12-28 Givaudan-Roure (International) S.A. Procédé pour la préparation de dodécahydro-3a,6,6,9a-tétraméthylnaphtho[2,1b]furanne et de dérivés d'haloéthyl-décaline
DE3942358A1 (de) * 1989-12-21 1991-06-27 Henkel Kgaa Verfahren zur herstellung von sclareolid
DE4123767A1 (de) * 1991-07-18 1993-01-21 Henkel Kgaa Verfahren zur herstellung von 8,12-oxido-13,14,15,16-tetranorlabdan
US5463089A (en) * 1994-07-22 1995-10-31 Quest International B.V. Preparation of ambrox
DE4439574A1 (de) * 1994-11-05 1996-05-09 Henkel Kgaa Verfahren zur Herstellung von 8alpha,12-Oxido-13,14,15,16-tetranorlabdan
EP0752423A1 (fr) * 1995-07-06 1997-01-08 Basf Aktiengesellschaft Procédé pour la préparation stéréosélective de (-)3a,6,6,9a-tétraméthyl-perhydronaphto(2,1-b)furanne

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000063200A1 (fr) * 1999-04-16 2000-10-26 Quest International B.V. Preparation d'oxyde de norlabdane
US6380404B1 (en) 1999-04-16 2002-04-30 Quest International B.V. Preparation of norlabdane oxide
GR1004177B (el) * 2001-07-05 2003-03-05 Βιορυλ Χημικη Και Γεωργικη Βιομηχανια, Επιστημονικη Ερευνα Α.Ε. Νεα μεθοδος συνθεσης (-) δωδεκαυδρο-3α,6,6,9α,-τετραμεθυλοναφθο (1,2β) φουρανιου
EP1710224A1 (fr) 2005-04-05 2006-10-11 Symrise GmbH & Co. KG Procédé pour la préparation de cétones par ozonolyse
US7335796B2 (en) 2005-04-05 2008-02-26 Symrise Gmbh & Co., Kg Process for the preparation of ketones by ozonolysis
WO2007036381A1 (fr) 2005-09-28 2007-04-05 Symrise Gmbh & Co. Kg Preparation d'aldehydes par ozonolyse d'alcools d'allyle secondaires
MD3889C2 (ro) * 2008-05-19 2009-11-30 Институт Химии Академии Наук Молдовы Procedeu de obţinere a 11-bishomodrim-8(9)-en-12-onei
MD4209C1 (ro) * 2012-03-30 2013-10-31 Институт Химии Академии Наук Молдовы Procedeu de obţinere a sclareoloxidului

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Publication number Publication date
EP0822191B1 (fr) 2001-09-19

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